A novel relative spacecraft attitude and position estimation approach based on an Unscented Kalman Filter (UKF) is derived. The integrated sensor suite comprises the gyro sensors on each spacecraft and a vision-based navigation system on the slave spacecraft. In the traditional algorithm, an assumption that the master's body frame coincides with its Local Vertical Local Horizontal (LVLH) frame is made to construct the line-of-sight observations for convenience. To solve this problem, two relative quaternions that map the master's LVLH frame to the slave and master body frames are involved. The general relative equations of motion for eccentric orbits are used to describe the positional dynamics. The implementation equations for the UKF are derived. A modified version of the UKF is presented based on the averaging-quaternion algorithm. Simulation results indicate that the proposed filters provide more accurate estimates of relative attitude and position than the Extended Kalman Filter (EKF).